Disulpho-1-amino-4-(oxy-, thio-, or aminosubstituted-monohalogenotriazinylamino-aryl-or arylazo-amino) anthraquinone dyestuffs



tinned states atenr ance meme,

hen l. R e c. 3,655,191 P Y 1 y repres nt an lkyl or substituted alkyl 1 w radical as exemplified above as a special case of sub- K %%%b% E st tuted alkyl, R and R may be oined together to form,

AM1N9 ARYL 9R ARYLAZSAMENU) ANTHRA with the nitrogen atom, a saturated heterocyclic radical QUENGNE DYESTUFEE 5 Such as N-morpholino.

Robert Norman Heslop and Charles Hugh Reece, Man- In the above fOTmula, X Preferably represents all chester, England, assignors to imperial Chemical inarylene brid ing group and in particular a bridging group dustries Limited, London, England, a corporation of such that the attached amino groups are linked to the Great Britain same or different arylene radicals preferably monocyclic N0 g Filed Jlliy 19539 749,341 arylene radicals, that is to say to phenylene or substituted Claims priority, application Great Britain July 22, 1957 phenylene radica1s Thus, X may reprssent for 6 cranes. ((31.269-153) ample, a group, a group a This invention relates to new anthroquinonoid dyee 4- C group each of which is subt fi d more i l l i relates to new h stitutcd by at least one anionic solubilising group such as quinonoid dyestuffs which possess excellent solubility and 15 a SUIPhOIIiC acid of carboxylic acid gfOllP and which y are valuable for the production of fast colourations on be further Subsliilltfld y for p y methOXy cellulosic textile materials. and 01110) gr 1 In our copending UK. application No. 34,501/54 and According to a further feature of the invention there th co rgspgnding bli h d Belgian ificatio N is provided a process for the manufacture of new anthra- 543,2l6, there are described new anthraquinonoid dyequinoiloid dyestuffs which comprises interacting a W studs Which, in the form of their free acids, are of the halide, 011 the one hand with all aminoathraquillone f l 7 compound of the formula:

(II) IIVHZ fi N112 .SO3II SOsH HOaS H033 ll o NHXNH-(|J (l1o1 0 NHl-NH N Formula 2 wherein X has the meaning given above, and on the 01 other hand With a compound of the formula H-Q-R wherein Q and R have the meanings given above, under such conditions that the resultant product still contains a halogen atom attached to the triazine ring.

wherein X stands for a bridging group containing at least one anionic solubilising group.

The present invention is a modification of or improvement in the invention described in the aforesaid applica- The amincanthmqllimnfs Q pi the abfwe tion. We have now found that valuable dyestuffs for P Q f r example, i-aHtlI'LO-i-(i-2lm1IlOtll1lllIlO)-Ell'ltfif2lcellulosic textile materials may be obtained by replacing A0 m f g 15jmsulphmiaFCICL may be obtained as the cyanuric chloride used in the process of the said scuba elglan speclficauon BR1543316- application by certain other dihalogeno-l:325-triazines. stultable compounds of the formula Q for use According to the prasem invention, We provide HEW 1n the above process include colourless primary or seeanthraquinonoid dyestuffs which, in the form of their ondanry ammsv hydroxy or mercapfo compPunds havlng free adds am represented by the formula: the Iormula RNHR ROH or RSH respectively. Exam- A 0 \TH pics of such compounds include, for example, methanol,

H ethanol, iso-butanol, octanol, betaethoxyethanol, cyclo- S H hexanol, benzyl alcohol, phenylethyl alcohol, phenol, 0-, 03 mand p-cresols, xylenols, chlorophenols, sulphophenols,

H038 dialkylaminophenols, sulphonapnthols, ammonia, methyl- V N amine, diethylamine, hydroxyethylamine, taurine, gly- II 7 1 cine, benzylamine, cyclohexylamine, aniline, toluidine, O fi chloroaniline, anisidine, aminoacetanilide, orthanilic, N metanilic and sulphanilic acids, thiophenol, thiocresol and p-sulphothiophenol.

I The process of the invention is advantageously carried Q-R 4 out 111 the presence of an acio-bindmg agent, preferably Formula 1 a carbonate or a bicarbonate. It is carried out under such wherein X stands for a bridging group containing at least Conditions that i116 final Pwduct Still Contains a Single one i i l bili i group, halogen atom attached to the triazine ring, that is, for

Y stands f hi i or b i m example, in an organic solvent or preferably at a rela- Q stands for an oxygen atom, a sulphur atom or a tively low temperature in an aqueous medium. In general, grouping of th formul NR d R and R may be the process is preferably carried out at a temperature bethe same or different and R stands for a hydrogen atom, w n 15 and 50 C. and at a pH between 4 and 7 in or a hydrocarbon or substituted hydrocarbon radical queous medium. having no dyestuff character and R stands for a hydro- The new anthraquinonoid dyes uffs may readily be gen atom or an alkyl or substituted alkyl radical. precipitated in the form of their sodium salts by adding As examples of hydrocarbon or substituted hydrocarcommon salt to the neutral aqueous medium, and may bon radicals repreesnted by R in the above formula, then be isolated for example, by filtration and drying. there may be mentioned alkyl or substituted alkyl, for The new anthraquinonoid dyestuffs are valuable dyeexample methyl and beta-ethoxyethyl, cycloalkyl, for stuffs for cellulose textile materials when applied in conexample cyclohexyl, aralkyl, for example benzyl, aryl, junction with an acid-binding agent, for example by the for example phenyl, tclyl, chlorophenyl and sulphoprocess described in Belgian specification No. 543,219,

wherein the coloured textile material is after-treated with an acid-binding agent, or by related processes wherein an acid-binding agent is applied to the textile material before or during the treatment with the dyestufi.

The new anthraquinonoid dyestuffs may also be used to colour textile materials of wool, silk and other natural protein fibres and also artificial fibres such as fibres of ardein, casein, polyamide or modified polyacrylonitrile, by the methods commonly used for the dyeing and printing of such textile materials, for example by treating the textile material with a hot neutral or weakly acid aqueous solution of the dyestufi.

When so applied the new anthraquinonoid dyestuffs give greenish-blue and green shades very fast to washing, and to light. The new anthraquinonoid dyestuffs have an advantage over the dyestuffs described in Belgian specification No. 543,216 in that they are more stable in the presence of acid-binding agents. Thus thickened printing pastes containing the new anthraquinonoid dyestuffs and an acid-binding agent are especially valuable for use in the printing process of Belgian specification No. 543,219.

The invention is illustrated but not limited by the following examples in which parts and percentages are by weight:

Example 1 A solution of 5.0 parts of 2:4-dichloro-6-methoxy-striazine in 24 parts of acetone is added gradually to a stirred mixture of 100 parts of water and 100 parts of crushed ice. The suspension so obtained is warmed to 30 C. and a solution of 15.9 parts of the trisodium salt of 1 amino 4 (4-aminoanilino) anthraquinone-2z3z5- trisulphonic acid in 250 parts of water is added during about 1 hour the temperature of the reaction mixture being maintained at from 30 to 32 C. during the addition. The mixture is then stirred for 45 minutes at the same temperature, then cooled to 20 C. and neutralised to litmus by the gradual addition of 10% aqueous sodium carbonate solution. Sufiicient sodium chloride is then added to the mixture to give a concentration of 200 grams per litre and the mixture is stirred until precipitation of the dyestufi is complete. The dyestuff is then filtered off, washed on the filter with 20% sodium chloride solution and dried at atmospheric temperature.

The dyestufi' so obtained forms a dark blue powder, possessing good solubility in water; when applied to cellulosic fibres by the methods described above, it yields greenish-blue shades having very good fastness to washing and to light.

Example 2 A solution of 15.9 parts of the trisodium salt of 1- amino 4 (4 aminoanilino)anthraquinone 2:3':5*trisulphonic acid in 300 parts of water is added slowly during 30 minutes to a stirred suspension of 4.6 parts of cyanuric chloride in 50 parts of acetone and 100 parts of water at 2 C. The reaction mixture during the addition is kept at between 0 and 5 by cooling and at a pH between 5 and 7 by the simultaneous addition of 2 N-sodium carbonate solution.

The reaction mixture is then stirred for one hour at from 2 to 5 C. The pH of the reaction mixture is then adjusted to 6 and 75 parts of sodium chloride are added. The mixture is filtered and the residue on the filter is washed with 200 parts of aqueous sodium chloride and then stirred with 800 parts of water and 3 parts of 27% aqueous ammonia solution for four hours at between 15 and C. and 120 parts of sodium chloride are added. The mixture is filtered and the residue on the filter is washed with 200 parts of 15 aqueous sodium chloride solution and dried at between 20 and C. The new anthraquinonoid dyestuff so obtained is a dark blue powder which dissolves in cold water giving a blue solution and in concentrated sulphuric acid giving a bluish red solution. When applied to cellulose fibres by the methods described above it gives greenish blue dyeings which have very good fastness to washing and to light.

Example 3 A solution of 4.48 parts of 2-beta-methoxyethoxy-4:6- dichloro-s-triazine in 100 parts of acetone is added to 500 parts of water keeping the temperature below 15 C. A solution of 16.78 parts of the tetra sodium salt of l-amino- 4 (4 [4-aminostyryl] anilino)-anthraquinone-2:2":3: S-tetrasulphonic acid in 1000 parts of water is added to this suspension during 30 minutes keeping the temperature between 15 and 20 C. and the reaction mixture is stirred for a further two hours at a temperature between 20 and 25 C. During this time 10% aqueous sodium carbonate solution is added to keep the pH of the reaction mixture between 5 and 7. The pH of the reaction mixture is finally adjusted to 7 and 250 parts of sodium chloride are added. The precipitated dyestufi is then filtered off, washed with 200 parts of 15% aqueous sodium chloride solution and dried at 20 C. The new dyestutf is obtained as a dark green powder which dissolves in sulphuric acid giving a bluish red solution and in water to give a greenish blue solution. It gives bluish green shades on cellulose fibres which have very good fastness to washing and to light.

Example 4 A solution of 14.22 parts of the tris-odium salt of 1- amino 4 (4' [4 aminophenyl] anilino) anthraquinone 2:3":5-trisul-phonic acid in 600 parts of water is added during 30 minutes to a stirred suspension of 3.69 parts of cyanuric chloride in 40 parts of acetone and parts of water at a temperature between 0 and 8 C., the pH being maintained between 5 and 7 by the addition of 10% aqueous sodium carbonate solution. The reaction mixture is stirred for two hours the pH of the solution being finally adjusted to 7. A solution of 3.9 parts of sodium metanilate in 20 parts of water is added and the reaction mixture is heated to a temperature between 30 and 35 C. and stirred for four hours, further quantities of 10% aqueous sodium carbonate solution being added to keep the pH between 7 and 8. The pH is finally adjusted to 8 and 40 parts of sodium chloride are added. The precipitated dyestufi is filtered off, washed with 200 parts of 5% aqueous sodium chloride solution and dried at 20 C. The new dyestutf is obtained as a dark green powder which dissolves in concentrated sulphuric acid to give a bluish red solution and in water to give a greenish blue solution. It gives greenish blue shades on cellulose which have very good fastness to washing and to light.

Example 5 To a solution of 15.66 parts of the trisodium salt of 1 amino 4 (4' [4":6" dichloro s triazin 2" yl-amino] anilino) anthraquinone-Z: 3 '15-trisulphonic acid (obtained as described in the first paragraph of Example 2) in 300 parts of water at 5 C. is added a solution of 3.46 parts of sodiuIn-4-acetylamino phenate in 20 parts of water during 1 hour. During the addition the temperature is allowed to rise to 20 C. The temperature is then raised to between 35 and 40 C. and the solution is stirred for 2 hours. 30 parts of sodium chloride are added and the precipitated dyestufi" is filtered ofi, washed with 200 parts of 10% aqueous sodium chloride solution and dried at 20 C. The new dyestufi is obtained as a dark blue powder which dissolves in concentrated sulphuric acid giving a bluish red solution and in water to give a greenish blue solution. It gives greenish blue shades on cellulose materials which have very good fastness to washing and to light.

The following table gives the shades of further example of the new anthraquinone dyestufis, obtained by reacting together substantially equimolecular proportions of the aminoanthr-aquinone compound of column I, the compound named in column 11 and cyanuric chloride.

What we claim is: 1. Dyestulfs which, in the form of their free acids, are represented by the formula:

(5-K wherein:

X is a radical selected from the group consisting of phenylene, biphenylene and phenylene azo phenylene radicals, each of which is substituted by a member selected from the class consisting of sulfonic acid and carboxylic acid groups;

One A stands for a sulfonic acid substituent and the other A stands for a hydrogen atom;

Y is selected from the group consisting of chlorine and bromine,

Q is selected from the group consisting of oxygen, sulfur, and -NH, and

R is selected from the group consisting of hydrogen,

lower alkyl, lower alkoxy-lower alkylene, and benzene radicals.

O NH:

SO H O1 HOnS fl) NH:

N/ \\N ('i NE Niel-y: c -NH.

NH: Hel s /C\\ l Net-O NH-C 0-01 soul 31 .l r

NH NH-i': 0-0011.

NH, solrr sons In N Hoas References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Grunthard: American Dyestufi Reporter, 1 an. 14, 1957,

German Application 1,017,303, printed Oct. 10, 1957 (Kl. 22b 3/02). 

1. DYESTUFFS WHICH, IN THE FORM OF THEIR FREE ACIDS, ARE REPRESENTED BY THE FORMULA: 